Compositions comprising tetrafluoeopropene &amp; carbon dioxide

ABSTRACT

Disclosed are compositions useful in a wide variety of applications, including heat transfer fluids which possess a highly desirable and unexpectedly superior combination of properties, and heat transfer systems and methods based on these fluids. The preferred heat transfer fluid comprises from about 1 to about 40 percent, on a weight basis, of carbon dioxide (CO 2 ) and from about 99 to about 60 percent, on a weight basis, of a compound having the Formula I XCF z R 3-z  (I), where X is a C 2  or a C 3  unsaturated, substituted or unsubstituted, alkyl radical, each R is independently Cl, F, Br, I or H, and z is 1 to 3. A preferred compound of Formula I is tetrafluoropropene, particularly 1,1,1,3-tetrafluoropropene and/or 1,1,1,3-tetrafluoropropene.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a Continuation-in-Part of U.S. applicationSer. No. 10/837,521 filed on Apr. 29, 2004.

The present application is also related to and incorporates by referenceeach of the following U.S. patent applications: U.S. application Ser.No. 10/837,525 filed Apr. 29, 2004; Ser. No. 10/837,526, filed Apr. 29,2004; Ser. No. 10/694,273, filed Oct. 27, 2003; Ser. No. 10/695,212,filed Oct. 27, 2003; Ser. No. 10/694,272 filed Oct. 27/2003.

The present application is related to and incorporates by reference eachof the following U.S. Provisional Applications: 60/567,426; 60/567,429;60/567,427; 60/567,425 and 60/567,428, all of which were filed on Apr.29, 2004.

FIELD OF THE INVENTION

This present invention relates to compositions comprising C₃fluoroolefins, particularly tetrafluoropropenes and carbon dioxide(CO₂).

BACKGROUND OF THE INVENTION

Fluorocarbon based fluids have found widespread use in industry in anumber of applications, including as refrigerants, aerosol propellants,blowing agents, heat transfer media, and gaseous dielectrics. Because ofthe suspected environmental problems associated with the use of some ofthese fluids, including the relatively high global warming potentialsassociated therewith, it is desirable to use fluids having low or evenzero ozone depletion potential, such as hydrofluorocarbons (“HFCs”).Thus, the use of fluids that do not contain chlorofluorocarbons (“CFCs”)or hydrochlorofluorocarbons (“HCFCs”) is desirable. Furthermore, someHFC fluids may have relatively high global warming potentials associatedtherewith, and it is desirable to use hydrofluorocarbon or otherfluorinated fluids having global warming potentials as low as possiblewhile maintaining the desired performance in use properties. However,the identification of new, environmentally-safe, mixtures is frequentlycomplicated by the need and/or desire to achieve a composition with sucha diverse set of properties.

With respect to heat transfer fluids, it is desirable in many differentsituations to selectively transfer heat between a fluid and a body to becooled or warmed. As used herein, the term “body” refers not only tosolid bodies but also other fluid materials, which take the shape of thecontainer in which they exist.

One well known system for achieving such transfer of heat achievescooling of a body by first pressurizing a vapor phase heat transferfluid and then expanding it through a Joule-Thomson expansion element,such as a valve, orifice, or other type of flow constriction. Any suchdevice will be referred to hereinafter simply as a Joule-Thompsonexpansion element, and systems using such an element are sometimesreferred to herein as Joule-Thompson systems. In most Joule-Thomsonsystems, single component, non-ideal gasses are pressurized and thenexpanded through a throttling component or expansion element, to producesubstantially isenthalpic cooling. The characteristics of the gas used,such as boiling point, inversion temperature, critical temperature, andcritical pressure effect the starting pressure needed to reach a desiredcooling temperature. While such characteristics are all generally wellknown and/or relatively easy to predict with an acceptable degree ofcertainty for single component fluids, this is not necessarily the casefor multi-component fluids

Because of the large number of properties or characteristics which arerelevant to the effectiveness and desirability of a heat transfer fluidin particular but to many other fluids in general, it is frequentlydifficult to predict in advance how any particular multi-component fluidwill perform as a heat transfer fluid. For example, U.S. Pat. No.5,774,052—Bivens discloses a combination of difluoroethane (HFC-32),pentafluoroethane (HFC-125) and a small amount (i.e., up to 5% byweight) of carbon dioxide (CO₂) in the form of an azeotropic fluid thatis said to have advantages as a refrigerant in certain applications.More particularly, the multi-component fluid of Bivens is said to benon-flammable and, due to its azeotropic nature, to undergo relativelylittle fractionation upon vaporization. However, applicants appreciatethat, the fluids of Bivens are comprised of relativelyhighly-fluorinated compounds, which are potentially environmentallydamaging from a global warming perspective. In addition, obtainingfluids with azeotropic properties can sometimes add significantly to thecost of such fluids when used as refrigerants.

U.S. Pat. No. 5,763,063—Richard et al. discloses a non-azeotropiccombination of various hydrocarbons, including HFC-32, and carbondioxide which form a fluid said to be acceptable as replacements forchlorodifluoromethane (HCFC-22). In particular, the Richard et al.patent teaches that the vapor pressure of this fluid is substantiallyequal to HCFC-22, which is only about 83 psia. Therefore, while thefluid of Richard et al. is expected to perform well in certainrefrigeration applications, it may be considered inadequate in the sametypes of applications mentioned above with respect to the Bivens fluid.

SUMMARY OF THE INVENTION

Applicants have discovered compositions which possess a highly desirableand unexpectedly superior combination of properties, particularly inconnection with heat transfer applications, systems and methods, butwhich also have advantage with respect to other uses, such as blowingagents, propellants and sterilizing agents for example. With respect toheat transfer applications, the present compositions may be used asrefrigerants in automotive air conditioning and heat pump systems, andin stationary air conditioning, heat pump and refrigeration systems,among others.

In preferred embodiments, the fluids of the present invention possessproperties that have heretofore been associated with CFCs, includingchemical stability, low toxicity, non-flammability, and efficiencyin-use, while at the same time substantially reducing or eliminating thedeleterious ozone depletion potential of such compositions. In addition,the preferred embodiments of the present invention provide compositionswhich also substantially reduce or eliminate the negative global warmingeffects associated with many compositions previously used as heattransfer fluids, blowing agents, propellants, sterilants, and others.This difficult to achieve combination of characteristics is important,for example, in low temperature air conditioning, refrigeration and heatpump applications, among others.

The present invention thus provides preferred composition comprisingfrom about 1 to about 40 percent, on a weight basis, of carbon dioxide(CO₂) and from about 60 to about 99 percent, on a weight basis, of acompound having the Formula I XCF_(z)R_(3-z) (I), where X is a C₂ or aC₃ unsaturated, substituted or unsubstituted, alkyl radical, each R isindependently Cl, F, Br, I or H, and z is 1 to 3. In preferredembodiments, the Formula (I) compound is tetrafluoropropene, morepreferably tetrafluoropropene selected from the group consisting of1,1,1,3-tetrafluoropropene (either cis or trans but preferablytransHFO-1234ze.), 1,1,1,2-tetrafluoropropene (HFO-1234yf, andcombinations of these. Compounds of Formula I are disclosed in copendingU.S. patent application Ser. No. 10/694,273, which is incorporatedherein by reference. Preferred compositions of the invention,particularly where the composition is a heat transfer fluid, comprisefrom about 5 to about 30 percent by weight of carbon dioxide (CO₂) andfrom about 70 to about 95 percent by weight of Formula I compound,preferably HFO-1234ze and/or HFO-1234yf. The preferred fluids of thepresent invention have a vapor pressure of at least about 30 psia at 35°F. The fluids are also preferably not azeotropic.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a graphical representation of the dew and bubble points ofcertain embodiments of the present compositions consisting oftransHFO-1234ze and CO₂ at about 32° F.

FIG. 2 is a graphical representation of the dew and bubble points ofcertain embodiments of the present compositions consisting oftransHFO-1234ze and CO₂ at 100° F.

FIG. 3 is a graphical representation of test results showing theperformance of certain embodiments of the present compositionsconsisting of transHFO-1234ze and CO₂ in comparison to previouscompositions.

FIG. 4 is a graphical representation of test results showing theperformance of certain embodiments of the present compositionsconsisting of transHFO-1234ze and CO₂ in comparison to previouscompositions.

FIG. 5 is a graphical representation of the dew and bubble points ofcertain embodiments of the present compositions consisting of HFO-1234yfand CO₂ of the present invention at about 32° F.

FIG. 6 is a graphical representation of the dew and bubble points ofcertain embodiments of the present compositions consisting of HFO-1234yfand CO₂ at about 100° F.

FIG. 7 is a graphical representation of test results showing theperformance of certain embodiments of the present compositionsconsisting of HFO-1234yf and CO₂ in comparison to previous compositions.

FIG. 8 is a graphical representation of test results showing theperformance of certain embodiments of the present compositionsconsisting of HFO-1234yf and CO₂ in comparison to previous compositions.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

The present inventors have developed compositions that help to satisfythe continuing need for alternatives to CFCs and HCFCs. According tocertain embodiments, the present invention provides compositionscomprising CO₂ and one or more tetrafluoropropene compounds, includingpreferably trans-1,1,1,3-tetrafluoropropene (“transHFO-1234ze”),cis-1,1,1,3-tetrafluoropropene (“cisHFO-1234ze”), HFO-1234yf andcombinations of these.

The term “HFO-1234” is used herein to refer to all tetrafluoropropenes.Among the tetrafluoropropenes are included HFO-1234yf and both cis- andtrans-1,1,1,3-tetrafluoropropene (HFO-1234ze). The term HFO-1234ze isused herein generically to refer to 1,1,1,3-tetrafluoropropene,independent of whether it is the cis- or trans-form. The terms“cisHFO-1234ze” and “transHFO-1234ze” are used herein to describe thecis- and trans-forms of 1,1,1,3-tetrafluoropropene respectively. Theterm “HFO-1234ze” therefore includes within its scope cisHFO-1234ze,transHFO-1234ze, and all combinations and mixtures of these.

Although the properties of cisHFO-1234ze and transHFO-1234ze differ inat least some respects, it is contemplated that each of these compoundsis adaptable for use, either alone or together with other compoundsincluding its stereoisomer, in connection with each of the compositions,applications, methods and systems described herein. For example, whiletransHFO-1234ze may be preferred for use in certain refrigerationsystems because of its relatively low boiling point (−19° C.), it isnevertheless contemplated that cisHFO-1234ze, with a boiling point of+9° C., also has utility in certain refrigeration systems of the presentinvention. Accordingly, it is to be understood that the terms“HFO-1234ze” and 1,1,1,3-tetrafluoropropene refer to both stereoisomers, and the use of this term is intended to indicate that each ofthe cis-and trans-forms applies and/or is useful for the stated purposeunless otherwise indicated.

HFO-1234 compounds are known materials and are listed in ChemicalAbstracts databases. The production of fluoropropenes such as CF₃CH═CH₂by catalytic vapor phase fluorination of various saturated andunsaturated halogen-containing C₃ compounds is described in U.S. Pat.Nos. 2,889,379; 4,798,818 and 4,465,786, each of which is incorporatedherein by reference. EP 974,571, also incorporated herein by reference,discloses the preparation of 1,1,1,3-tetrafluoropropene by contacting1,1,1,3,3-pentafluoropropane (HFC-245fa) in the vapor phase with achromium-based catalyst at elevated temperature, or in the liquid phasewith an alcoholic solution of KOH, NaOH, Ca(OH)₂ or Mg(OH)₂. Inaddition, methods for producing compounds in accordance with the presentinvention are described generally in connection with pending U.S. patentapplication entitled “Process for Producing Fluoropropenes” bearingattorney docket number (H0003789 (26267)), which is also incorporatedherein by reference.

In addition, applicants have recognized that the present compositions,and, preferably compositions in which the combination of HFO-1234 andCO₂ together comprise at least about 50% by weight of the composition,exhibit properties that make that make them advantageous for use as, orin, numerous applications, including as heat transfer compositions(including as refrigerants in automotive air conditioning and heat pumpsystems, and in stationary air conditioning, heat pump and refrigerationsystems), blowing agents, propellants, sterilizing agents and others.Accordingly, in yet other embodiments, the present invention providescompositions and methods associated with these and other uses.

The present compositions, particularly those comprising HFO-1234yf,HFO-1234ze and combinations of these, are believed to possess propertiesthat are advantageous for a number of important reasons. For example,applicants believe, based at least in part on mathematical modeling,that the fluoroolefins of the present invention will not have asubstantial negative affect on atmospheric chemistry, being negligiblecontributors to ozone depletion in comparison to some other halogenatedspecies. The preferred compositions of the present invention thus havethe advantage of not contributing substantially to ozone depletion. Thepreferred compositions also do not contribute substantially to globalwarming compared to many of the hydrofluoroalkanes presently in use.

In certain preferred forms, compositions of the present invention have aGlobal Warming Potential (GWP) of not greater than about 1000, morepreferably not greater than about 500, and even more preferably notgreater than about 150. In certain embodiments, the GWP of the presentcompositions is not greater than about 100 and even more preferably notgreater than about 75. As used herein, “GWP” is measured relative tothat of carbon dioxide and over a 100-year time horizon, as defined in“The Scientific Assessment of Ozone Depletion, 2002, a report of theWorld Meteorological Association's Global Ozone Research and MonitoringProject,” which is incorporated herein by reference.

In certain preferred forms, the present compositions also preferablyhave an Ozone Depletion Potential (ODP) of not greater than 0.05, morepreferably not greater than 0.02 and even more preferably about zero. Asused herein, “ODP” is as defined in “The Scientific Assessment of OzoneDepletion, 2002, A report of the World Meteorological Association'sGlobal Ozone Research and Monitoring Project,” which is incorporatedherein by reference.

The amount of the Formula I compounds, particularly HFO-1234, containedin the present compositions can vary widely, depending the particularapplication, and compositions containing more than trace amounts andless than 100% of the compound are within broad the scope of the presentinvention. In preferred embodiments, the present compositions compriseHFO-1234, preferably HFO-1234yf and/or HFO-1234ze, in amounts from about5% by weight to about 99% by weight, and even more preferably from about5% to about 95%. Many additional compounds may be included in thepresent compositions, and the presence of all such compounds is withinthe broad scope of the invention. In certain preferred embodiments, thepresent compositions include, in addition to HFO-1234ze and/orHFO-1234yf, one or more of the following:

Trichlorofluoromethane (CFC-11)

Dichlorodifluoromethane (CFC-12)

Difluoromethane (HFC-32)

Pentafluoroethane (HFC-125)

1,1,2,2-tetrafluoroethane (HFC-134)

1,1,1,2-Tetrafluoroethane (HFC-134a)

Difluoroethane (HFC-152a)

1,1,1,2,3,3,3-Heptafluoropropane (HFC-227ea)

1,1,1,3,3,3-hexafluoropropane (HFC-236fa)

1,1,1,3,3-pentafluoropropane (HFC-245fa)

1,1,1,3,3-pentafluorobutane (HFC-365mfc)

water

The relative amount of any of the above noted components, as well as anyadditional components which may be included in present compositions, canvary widely within the general broad scope of the present inventionaccording to the particular application for the composition, and allsuch relative amounts are considered to be within the scope hereof.

Accordingly, applicants have recognized that certain compositions of thepresent invention can be used to great advantage in a number ofapplications. For example, included in the present invention are methodsand compositions relating to heat transfer applications, foam andblowing agent applications, propellant applications, sprayablecompositon applications, sterilaztion applications, and others. Thepresent compositions are generally useful as replacements for CFCs, suchas dichlorodifluormethane (CFC-12), HCFCs, such as chlorodifluoromethane(HCFC-22), HFCs, such as tetrafluoroethane (HFC-134a), and combinationsof HFCs and CFCs, such as the combination of CFC-12 and1,1-difluorethane (HFC-152a) (the combination CFC-12:HFC-152a in a73.8:26.2 mass ratio being known as R-500) in refrigerant, aerosol, andother applications.

According to certain preferred embodiments, the compositions of thepresent invention comprise, and preferably consist essentially of,effective amounts of HFO-1234 and CO₂. The term “effective amounts” asused herein refers to the amount of each component which uponcombination with the other component(s), results in the formation of acomposition having the desired properties, characteristics andfunctionality. It is believed that the amount of each compound requiredto provide an effective amount can be readily determined by thoseskilled in the art in view of the teachings contained herein withoutundue experimentation.

Applicants believe that, in general, the compositions of the presentinvention are generally effective and exhibit utility as refrigerantcompositions, blowing agent compositions, compatibilizers, aerosols,propellants, fragrances, flavor formulations, and solvent compositions,among others.

The Heat Transfer Fluids

The heat transfer compositions of the present invention are generallyadaptable for use in heat transfer applications, that is, as a heatingand/or cooling medium. Although it is contemplated that the compositionsof the present invention may include, in widely ranging amounts,compounds and/or components in addition to the fluoroolefins and CO₂, itis generally preferred that heat transfer compositions of the presentinvention, including refrigerant compositions, consist essentially of,and in some embodiments consist of fluorolefin of Formula I and CO₂.

The preferred heat transfer fluids comprise, and in certain preferredembodiments consist essentially of, HFO-1234 and CO₂. In certainpreferred embodiments the compositions consist essentially of HFO-1234zeand CO₂, and in other preferred embodiments the compositions consistessentially of HFO-1234yf and CO₂. The relative amount of thehydrofluoroolefin used in accordance with the present invention ispreferably selected to produce a heat transfer fluid which has therequired heat transfer capacity, particularly refrigeration capacity,and preferably is at the same time non-flammable. As used herein, theterm non-flammable refers to a fluid which is non-flammable in allproportions in air as measured by ASTM E-681.

In certain embodiments, such as those in which both performance andnon-flammability are especially important, it is preferred that the heattransfer fluid comprise, and preferably consist of, from about 1 toabout 40 wt % CO₂ and from about 60 to about 99 wt. % Formula Icompound, preferably HFO-1234ze and/or HFO-1234yf, with fluidscomprising from about 5 to about 35 wt. % CO₂ and from about 65 to about95 wt % of HFO-1234ze and/or HFO-1234yf, being even more preferred. Inhighly preferred embodiments, the heat transfer fluid consistsessentially of, and in certain embodiments consists of, HFO-1234ze andCO₂. In certain other highly preferred embodiments, the heat transferfluid consists essentially of, and in certain embodiments consists of,HFO-1234yf and CO₂.

The heat transfer fluids of the present invention are adaptable for usein a wide variety of heat transfer applications, and all suchapplications are within the scope of the present invention. The presentfluids find particular advantage and unexpectedly beneficial propertiesin connection with applications that require and/or can benefit from theuse of highly efficient, non-flammable refrigerants that exhibit low ornegligible global warming effects, and low or no ozone depletionpotential. The present fluids also provide advantage to low temperaturerefrigeration applications, such as those in which the refrigerant isprovided at a temperature of about −20° C. or less and which haverelatively high cooling power. The preferred heat transfer fluids arehighly efficient in that they exhibit a coefficient of performance (COP)that is high relative to the COP of the individual components of thefluid and/or relative to many refrigerants which have previously beenused. The term COP is well known to those skilled in the art and isbased on the theoretical performance of a refrigerant at specificoperating conditions as estimated from the thermodynamic properties ofthe refrigerant using standard refrigeration cycle analysis techniques.See, for example, “Fluorocarbons Refrigerants Handbook”, Ch. 3,Prentice-Hall, (1988), by R. C. Downing, which is incorporated herein byreference. The coefficient of performance, COP, is a universallyaccepted measure, especially useful in representing the relativethermodynamic efficiency of a refrigerant in a specific heating orcooling cycle involving evaporation or condensation of refrigerant. COPis related to or a measure of the ratio of useful refrigeration to theenergy applied by the compressor in compressing the vapor and thereforeexpresses the capability of a given compressor to pump quantities ofheat for a given volumetric flow rate of a heat transfer fluid, such asa refrigerant. In other words, given a specific compressor, arefrigerant with a higher COP will deliver more cooling or heatingpower.

Similarly the cooling capacity of a refrigerant is also an importantparameter and can be estimated from the thermodynamic properties of therefrigerant. If the refrigerant is to be used in a system designed foranother refrigerant, the capacity of the two refrigerants should besimilar, in order to obtain a similar performance and to minimize thesystem adjustments and/or modifications needed as part of thereplacement process. Among the common refrigerants being used inrefrigeration and air conditioning/heat pumps, and which may be replacedby the compositions of the present invention, are R-507A, R-404A, R-22,R-407C and R-410A. The applicants have found that various composition ofthis invention can be used in the applications where these refrigerantsare used with slight adjustments in composition.

In certain preferred embodiments, the compositions of the presentinvention are used in refrigeration systems originally designed for usewith an HFC refrigerant, such as, for example, HFC-134a, or an HCFCrefrigerant, such as, for example, HCFC-22. The preferred compositionsof the present invention tend to exhibit many of the desirablecharacteristics of HFC-134a and other HFC refrigerants, including a GWPthat is as low, or lower than that of conventional HFC refrigerants, anda capacity that is substantially similar to or substantially matches,and preferably is as high as or higher than such refrigerants. Inparticular, applicants have recognized that the preferred compositionsof the present invention tend to exhibit relatively low global warmingpotentials (“GWPs”), preferably less than about 1000, more preferablyless than about 500, and even more preferably less than about 150.Certain embodiments are particularly desirable as alternatives to orreplacements for certain conventional HFCs, such as R-404A orcombinations of HFC-32, HFC-125 and HFC-134a (the combinationHFC-32:HFC-125:HFC134a in approximate 23:25:52 weight ratio is referredto as R-407C), for use as refrigerants in many applications. Heattransfer compositions of the present invention are particularlypreferred as alternates to or replacements for HFC-32, HFC-125,HFC-134a, HFC-143a, HFC-152a, HFC-22, R-12 and R-500.

In certain other preferred embodiments, the present compositions areused in heat transfer systems in general, and in refrigeration systemsin particular, originally designed for use with a CFC-refrigerant. Asused herein the term “refrigeration system” refers generally to anysystem or apparatus, or any part or portion of such a system orapparatus, which employs a refrigerant to provide cooling. Suchrefrigeration systems include, for example, air conditioners, electricrefrigerators, chillers (including chillers using centrifugalcompressors), transport refrigeration systems, commercial refrigerationsystems and the like.

In certain preferred embodiments, the present compositions, particularlycompositions in the form of heat transfer fluids generally andrefrigerants in particular, further comprise a lubricant. Any of avariety of conventional and unconventional lubricants may be used in thecompositions of the present invention. An important requirement for thelubricant is that, when in use in a refrigerant system, there must besufficient lubricant returning to the compressor of the system such thatthe compressor is lubricated. Thus, suitability of a lubricant for anygiven system is determined partly by the refrigerant/lubricantcharacteristics and partly by the characteristics of the system in whichit is intended to be used. Examples of suitable lubricants, which aregenerally those commonly used in refrigeration machinery using ordesigned to use hydrofluorocarbon (HFC) refrigerants, chloroflurocarbonrefrigerants and hydrochlorofluorocarbons refrigerants, include mineraloil, silicone oil, polyalkyl benzenes (sometimes referred to as PABs),polyol esters (sometimes referred to as POEs), polyalkylene glycols(sometimes referred to as PAGs), polyalkylene glycol esters (sometimesreferred to as PAG esters), polyvinyl ethers (sometimes referred to asPVEs), poly(alpha-olefin) (sometimes referred to as PAOs), andhalocarbon oils, particularly poly(chlorotrifluorethylene) and the like.Mineral oil, which comprises paraffin oil or naphthenic oil, iscommercially available. Commercially available mineral oils includeWitco LP 250 (registered trademark) from Witco, Zerol 300 (registeredtrademark) from Shrieve Chemical, Sunisco 3GS from Witco, and CalumetR015 from Calumet. Commercially available polyalkyl benzene lubricantsinclude Zerol 150 (registered trademark). Commercially available estersinclude neopentyl glycol dipelargonate which is available as Emery 2917(registered trademark) and Hatcol 2370 (registered trademark).Commercially available PAGs include Motorcraft PAG RefrigerantCompressor Oil, available from Ford, with similar products beingavailable from Dow. Commercially available PAOs include CP-4600 from CPIEngineering. Commercially available PVEs are available from IdemitsuKosan. Commercially available PAG esters are available from Chrysler.Other useful esters include phosphate esters, dibasic acid esters, andfluoroesters.

For refrigeration systems using or designed to use HFCs, it is generallypreferred to use as lubricants PAGs, PAG esters, PVEs, and POEs,particularly for systems comprising compression refrigeration,air-conditioning (especially for automotive air conditioning) and heatpumps. For refrigeration systems using or designed to use CFCs or HCFCs,it is generally preferred to use as lubricants mineral oil or PAB. Incertain preferred embodiments, the lubricants of this invention areorganic compounds which are comprised of carbon, hydrogen and oxygenwith a ratio of oxygen to carbon which provides, in combination with theamounts used, effective solubility and/or miscibility with therefrigerant to ensure sufficient return of the lubricant to thecompressor. This solubility or miscibility preferably exists at at leastone temperature from about −30° C. and 70° C.

PAGs and PAG esters are highly preferred in certain embodiments becausethey are currently in use in particular applications such as originalequipment mobile air-conditioning systems. Polyol esters are highlypreferred in other certain embodiments because they are currently in usein particular non-mobile applications such as residential, commercial,and industrial air conditioning and refrigeration. Of course, differentmixtures of different types of lubricants may be used.

Many existing refrigeration systems are currently adapted for use inconnection with existing refrigerants, and the compositions of thepresent invention are believed to be adaptable for use in many of suchsystems, either with or without system modification. In manyapplications the compositions of the present invention may provide anadvantage as a replacement in smaller systems currently based on certainrefrigerants, for example those requiring a small refrigerating capacityand thereby dictating a need for relatively small compressordisplacements. Furthermore, in embodiments where it is desired to use alower capacity refrigerant composition of the present invention, forreasons of efficiency for example, to replace a refrigerant of highercapacity, such embodiments of the present compositions provide apotential advantage. Thus, it is preferred in certain embodiments to usecompositions of the present invention, particularly compositionscomprising a substantial proportion of, and in some embodimentsconsisting essentially of the present compositions, as a replacement forexisting refrigerants, such as: HFC-134a; CFC-12; HCFC-22; HFC-152a;combinations of pentfluoroethane (HFC-125), trifluorethane (HFC-143a)and tetrafluoroethane (HFC-134a) (the combinationHFC-125:HFC-143a:HFC134a in approximate 44:52:4 weight ratio is referredto as R-404A); combinations of HFC-32, HFC-125 and HFC-134a (thecombination HFC-32:HFC-125:HFC134a in approximate 23:25:52 weight ratiois referred to as R-407C); combinations of methylene fluoride (HFC-32)and pentfluoroethane (HFC-125) (the combination HFC-32:HFC-125 inapproximate 50:50 weight ratio is referred to as R-410A and also asAZ-20); the combination of CFC-12 and 1,1-difluorethane (HFC-152a) (thecombination CFC-12:HFC-152a in a 73.8:26.2 weight ratio is referred toR-500); and combinations of HFC-125 and HFC-143a (the combinationHFC-125:HFC143a in approximate 50:50 weight ratio is referred to asR-507A). In certain embodiments it may also be beneficial to use thepresent compositions in connection with the replacement of refrigerantsformed from the combination HFC-32:HFC-125:HFC134a in approximate20:40:40 weight ratio, which is referred to as R-407A, or in approximate15:15:70 weight ratio, which is referred to as R-407D. The presentcompositions are also believed to be suitable as replacements for theabove noted compositions in other applications, such as aerosols,blowing agents and the like.

In certain applications, the refrigerants of the present inventionpotentially permit the beneficial use of larger displacementcompressors, thereby resulting in better energy efficiency than otherrefrigerants, such as HFC-134a. Therefore the refrigerant compositionsof the present invention provide the possibility of achieving acompetitive advantage on an energy basis for refrigerant replacementapplications.

It is contemplated that the compositions of the present also haveadvantage (either in original systems or when used as a replacement forrefrigerants such as CFC-12, HCFC-22, HFC-134a, HFC-152a, R-500 andR-507A), in chillers typically used in connection with commercial airconditioning and refrigeration systems. In certain of such embodimentsit is preferred to including in the present compositions from about 0.5%to about 30% of a supplemental flammability suppressant, and in certaincases more preferably 0.5% to about 15% by weight and even morepreferably from about 0.5 to about 10% on a weight basis. In this regardit is noted that the CO₂ and HFO-1234 components of the presentcompositions may in certain embodiments act as flammability suppressantswith respect to other components in the composition. For example, CO₂ isbelieved to function to suppress the flammability of HFO-1234ze. Incases where other components more flammable are included in thecomposition, HFO1234-ze and CO₂ may each function to suppress theflammability of such other component. Thus, components other thanHFO1234-ze and CO₂ which have flammability suppressant functionality inthe composition will sometimes be referred to herein as a supplementalflammability suppressant.

In certain embodiments, co-refrigerants, including for example HFCs,HCFCs and CFCs may be included in the heat transfer compositions of thepresent invention, including one or more of the following, including anyand all isomers thereof:

Trichlorofluoromethane (CFC-11)

Dichlorodifluoromethane (CFC-12)

Difluoromethane (HFC-32)

Pentafluoroethane (HFC-125)

1,1,2,2-tetrafluoroethane (HFC-134)

1,1,1,2-Tetrafluoroethane (HFC-134a)

Difluoroethane (HFC-152a)

1,1,1,2,3,3,3-Heptafluoropropane (HFC-227ea)

1,1,1,3,3,3-hexafluoropropane (HFC-236fa)

1,1,1,3,3-pentafluoropropane (HFC-245fa)

1,1,1,3,3-pentafluorobutane (HFC-365mfc)

water

The relative amount of any of the above noted components, as well as anyadditional components which may be included in present compositions, maybe incorporated in amounts depending on the particular application forthe composition, and all such relative amounts are considered to bewithin the scope hereof.

The present methods, systems and compositions are thus adaptable for usein connection with automotive air conditioning systems and devices,commercial refrigeration systems and devices, chillers (includingsystems which utilize centrifugal compressors), residential refrigeratorand freezers, general air conditioning systems, heat pumps, and thelike.

As mentioned before, any additional components (such as stabilizers,passivators, and the like) not specifically mentioned herein but knownto those skilled in the art may be added to the composition to tailorthe properties to the need.

Heat Transfer Methods and Systems

The method aspects of the present invention comprise transferring heatto or from a body using a heat transfer fluid in accordance with thepresent invention. Sensible heat transfer and/or heat transfer by meansof evaporation or condensation are within the scope of the presentinvention. Those skilled in the art will appreciate that many knownmethods may adapted for use with the present invention in view of theteachings contained herein, and all such methods are within the broadscope hereof. For example, vapor compressions cycles are methodscommonly used for refrigeration and/or air conditioning. In its simplestform, the vapor compression cycle involves providing the present heattransfer fluid in liquid form and changing the refrigerant from theliquid to the vapor phase through heat absorption, generally atrelatively low pressure, and then from the vapor to the liquid phasethrough heat removal, generally at an elevated pressure. In suchembodiments, the refrigerant of the present invention is vaporized inone or more vessels, such as an evaporator, which is in contact,directly or indirectly, with the body to be cooled. The pressure in theevaporator is such that vaporization of the heat transfer fluid takesplace at a temperature below the temperature of the body to be cooled.Thus, heat flows from the body to the refrigerant and causes therefrigerant to vaporize. The heat transfer fluid in vapor form is thenremoved, preferably by means of a compressor or the like which at oncemaintains a relatively low pressure in the evaporator and compresses thevapor to a relatively high pressure. The temperature of the vapor isalso generally increased as a result of the addition of mechanicalenergy by the compressor. The high pressure vapor then passes to one ormore vessels, preferably a condenser, whereupon heat exchange with alower temperature medium removes the sensible and latent heats,producing subsequent condensation. The liquid refrigerant, optionallywith further cooling, then passes to the expansion valve and is ready tocycle again.

In one embodiment, the present invention provides a method fortransferring heat from a body to be cooled to the present heat transferfluid comprising compressing the fluid in a centrifugal chiller, whichmay be single or multi-stage. As used herein, the term “centrifugalchiller” refers to one or more pieces of equipment which cause anincrease in the pressure of the present heat transfer fluid.

Certain preferred methods for heating a fluid or body comprisecondensing a refrigerant composition comprising an azeotrope-likecomposition of the present invention in the vicinity of the fluid orbody to be heated and thereafter evaporating said refrigerantcomposition. In light of the disclosure herein, those of skill in theart will be readily able to heat and cool articles according to thepresent inventions without undue experimentation.

Applicants have found that in the systems of the present invention manyof the important refrigeration system performance parameters arerelatively close to the parameters for referigerants such as R-134a,HCFC-22, R-407C, R-410A and combinations of these. Since many existingrefrigeration systems have been designed for these referigerants,particularly R-134a, or for other refrigerants with properties similarto these, those skilled in the art will appreciate the substantialadvantage of a low GWP and/or a low ozone depleting refrigerant that canbe used as replacement for R-134a, HCFC-22, R-407C, R-410A or likerefrigerants with relatively minimal modifications to the system. It iscontemplated that in certain embodiments the present invention providesretrofitting methods which comprise replacing the refrigerant in anexisting system with a composition of the present invention, withoutsubstantial modification of the system. In certain preferred embodimentsthe replacement step is a drop-in replacement in the sense that nosubstantial redesign of the system is required and no major item ofequipment needs to be replaced in order to accommodate the refrigerantof the present invention. In certain preferred embodiments, the methodscomprise a drop-in replacement in which the capacity of the system is atleast about 70%, preferably at least about 85%, and even more preferablyat least about 90% of the system capacity prior to replacement. Incertain preferred embodiments, the methods comprise a drop-inreplacement in which the suction pressure and/or the discharge pressureof the system, and even more preferably both, is/are at least about 70%,more preferably at least about 90% and even more preferably at leastabout 95% of the system capacity prior to replacement. In certainpreferred embodiments, the methods comprise a drop-in replacement inwhich the mass flow of the system is at least about 80%, and even morepreferably at least 90% of the system capacity prior to replacement.

In certain preferred embodiments, the methods for cooling, includingcooling of other fluid either directly or indirectly or a body directlyor indirectly, comprise condensing the present refrigerant compositionand thereafter evaporating said refrigerant composition in the vicinityof the fluid or body to be cooled. As used herein, the term “body” isintended to refer not only to inanimate objects but also to livingtissue, including animal tissue in general and human tissue inparticular. For example, certain aspects of the present inventioninvolve application of the present composition to human tissue for oneor more therapeutic purposes, such as a pain killing technique, as apreparatory anesthetic, or as part of a therapy involving reducing thetemperature of the body being treated. In certain embodiments, theapplication to the body comprises providing the present compositions inliquid form under pressure, preferably in a pressurized container havinga one-way discharge valve and/or nozzle, and releasing the liquid fromthe pressurized container by spraying or otherwise applying thecomposition to the body. As the liquid evaporates from the surface beingsprayed, the surface cools.

The present invention also provides methods, systems and apparatus forcooling of objects or very small portions of objects to very lowtemperatures, sometimes referred to herein for the purposes ofconvenience, but not by way of limitation, as micro-freezing. Theobjects to be cooled in accordance with the present micro-freezingmethods may include not only inanimate matter (eg., electroniccomponents), but also animate matter (biological matter) In certainembodiments, the invention provides for selective cooling of a verysmall or even microscopic object to a very low temperature withoutsubstantially affecting the temperature of surrounding objects. Suchmethods, which are sometimes referred to herein as “selectivemicro-freezing,” are advantageous in several fields, such as for examplein electronics, where it may be desirable to apply cooling to aminiature component on a circuit board without substantially coolingadjacent components. Such methods may also provide advantage in thefield of medicine, where it may be desirable cool miniature discreteportions of biological tissue to very low temperatures in theperformance of medical techniques, including for anesthetic purposes,pain killing purposes, therapeutic purposes (eg., cryosurgery),preferably without substantially cooling adjacent tissues.

Cryosurgery methods of the present invention include, but are notlimited to, medical (such as gynecology, dermatology, neurosurgery andurology), dental, and veterinary procedures. Unfortunately, currentlyknown instruments and methods for selective micro-freezing have severallimitations which make their use difficult or impossible in such fields.Specifically, known systems do not always have sufficient precision andflexibility to allow their widespread use in endoscopic and percutaneouscryosurgery.

One major advantage of the present methods and systems is the ability toprovide relatively low temperature cooling with systems and methods thatrequire relatively simple equipment and/or require only moderatelyelevated pressures. By way of contrast, typical prior art cryosurgicalmethods used liquid nitrogen or nitrous oxide as coolant fluids. Liquidnitrogen is usually either sprayed onto the tissue to be destroyed, orit is circulated to cool a probe which is applied to the tissue. Liquidnitrogen has an extremely low temperature of approximately 77° K., and ahigh cooling capacity, making it very desirable for this purpose.However, liquid nitrogen typically evaporates and escapes to theatmosphere during use, requiring the continual replacement of storagetanks. Further, since the liquid is so cold, the probes and otherequipment used for its application require vacuum jackets or other typesof insulation to protect the surrounding tissue. This makes the probesrelatively complex, bulky, and rigid, and therefore unsuitable forendoscopic or intravascular use. The need for relatively bulky supplyhoses and the progressive cooling of all the related components make theliquid nitrogen instruments less than comfortable for the physician, aswell, and they can cause undesired tissue damage. Furthermore, nitrousoxide systems used in cryosurgery pressurize the gas to 700 to 800 psiain order to reach practical cooling temperatures of no lower than about190° K. to 210° K. In the preferred systems and methods of the presentinvention, particularly cooling apparatus use in the production oflasers, superconductors and electronics, and in cryosurgery, the systemand methods operate effectively and with a high degree of efficiencyusing a heat transfer fluid of the present invention and a fluidlet-down pressure less than about 420 psia.

Propellant and Aerosol Compositions

In another embodiment, the compositions of this invention may be used aspropellants in sprayable compositions, either alone or in combinationwith known propellants. The propellant composition comprises, morepreferably consists essentially of, and, even more preferably, consistsof the compositions of the invention. The active ingredient to besprayed together with inert ingredients, solvents, and other materialsmay also be present in the sprayable mixture. Preferably, the sprayablecomposition is an aerosol. Suitable active materials to be sprayedinclude, without limitation, cosmetic materials such as deodorants,perfumes, hair sprays, cleansers, and polishing agents as well asmedicinal materials and/or biologically active materials, such asanti-asthma and any other medication or the like, including preferablyany other medicament or agent intended to be inhaled.

The medicament or other therapeutic agent is preferably present in thecomposition in a therapeutic amount, with a substantial portion of thebalance of the composition comprising a compound of Formula I of thepresent invention, preferably HFO-1234, and even more preferablyHFO-1234yf and/or HFO-1234ze.

Aerosol products for industrial, consumer or medical use typicallycontain one or more propellants along with one or more activeingredients, inert ingredients or solvents. The propellant provides theforce that expels the product in aerosolized form. While some aerosolproducts are propelled with compressed gases like carbon dioxide,nitrogen, nitrous oxide and even air, most commercial aerosols useliquefied gas propellants. The most commonly used liquefied gaspropellants are hydrocarbons such as butane, isobutane, and propane.Dimethyl ether and HFC-152a (1,1-difluoroethane) are also used, eitheralone or in blends with the hydrocarbon propellants. Unfortunately, allof these liquefied gas propellants are highly flammable and theirincorporation into aerosol formulations will often result in flammableaerosol products.

Applicants have come to appreciate the continuing need for nonflammable,liquefied gas propellants with which to formulate aerosol products. Thepresent invention provides compositions of the present invention,particularly and preferably compositions comprising CO₂ and HFO-1234,and even more preferably HFO-1234yf and/or HFO-1234ze, for use incertain industrial aerosol products, including for example spraycleaners, lubricants, and the like, and in medicinal aerosols, includingfor example to deliver medications to the lungs or mucosal membranes.Examples of this includes metered dose inhalers (MDIs) for the treatmentof asthma and other chronic obstructive pulmonary diseases and fordelivery of medicaments to accessible mucous membranes or intranasally.The present invention thus includes methods for treating ailments,diseases and similar health related problems of an organism (such as ahuman or animal) comprising applying a composition of the presentinvention containing a medicament or other therapeutic component to theorganism in need of treatment. In certain preferred embodiments, thestep of applying the present composition comprises providing a MDIcontaining the composition of the present invention (for example,introducing the composition into the MDI) and then discharging thepresent composition from the MDI.

The compositions of the present invention, particularly compositionscomprising or consisting essentially of CO₂ and HFO-1234 (preferablyHFO-1234yf, HFO-1234ze and combinations thereof), are capable ofproviding nonflammable, liquefied gas propellant and aerosols that donot contribute substantially to global warming. The present compositionscan be used to formulate a variety of industrial aerosols or othersprayable compositions such as contact cleaners, dusters, lubricantsprays, and the like, and consumer aerosols such as personal careproducts, household products and automotive products. The presentcompositions are particularly preferred for use as an importantcomponent of propellant compositions for in medicinal aerosols such asmetered dose inhalers. The medicinal aerosol and/or propellant and/orsprayable compositions of the present invention in many applicationsinclude, in addition to CO₂ and a compound of formula (I) or (II)(preferably HFO-1234), a medicament such as a beta-agonist, acorticosteroid or other medicament, and, optionally, other ingredients,such as surfactants, solvents, other propellants, flavorants and otherexcipients. The compositions of the present invention, unlike manycompositions previously used in these applications, have goodenvironmental properties and are not considered to be potentialcontributors to global warming or ozone depletion. The presentcompositions therefore provide in certain preferred embodimentssubstantially nonflammable, liquefied gas propellants having very lowGlobal Warming potentials and/or low ozone depletions, as describedabove.

Blowing Agents, Foams, Foamable Compositions and Foaming Methods

Yet another embodiment of the present invention relates to blowingagents comprising a composition of the present invention. In oneembodiment, the blowing agent comprises, and preferably consistsessentially of, compositions of the present invention. In general, theblowing agent may include the compositions of the present invention inwidely ranging amounts. It is generally preferred, however, that theblowing agents comprise compound(s) of formula I and CO₂, with amount ofthese components together comprising at least about 5% by weight, andeven more preferably at least about 15% by weight, of the blowing agent.In certain preferred embodiments, the compound(s) of formula I and CO₂together comprises at least about 50% by weight of the blowing agent,and in certain embodiments the blowing agent consists essentially ofcompound(s) of formula I and CO₂.

In certain preferred embodiments, the blowing agent includes, inaddition to compound(s) of formula I and CO₂, one or more of co-blowingagents, fillers, vapor pressure modifiers, flame suppressants,stabilizers and like adjuvants.

In other embodiments, the invention provides foamable compositions. Thefoamable compositions of the present invention generally include one ormore components capable of forming foam having a generally cellularstructure and a blowing agent in accordance with the present invention.In certain embodiments, the one or more components comprise athermosetting composition capable of forming foam and/or foamablecompositions. Examples of thermosetting compositions includepolyurethane and polyisocyanurate foam compositions and also phenolicfoam compositions. In such foam embodiments, one or more of the presentcompositions are included as a blowing agent in a foamable composition,which composition preferably includes one or more additional componentscapable of reacting and foaming, or as a part of a premix containing oneor more parts of the foamable composition, which preferably includes oneor more of the components capable of reacting and/or foaming under theproper conditions to form a foam or cellular structure, as is well knownin the art.

Any of the methods well known in the art, such as those described in“Polyurethanes Chemistry and Technology,” Volumes I and II, Saunders andFrisch, 1962, John Wiley and Sons, New York, N.Y., which is incorporatedherein by reference, may be used or adapted for use in accordance withthe foam embodiments of the present invention. For example, the CO₂ ofthis composition may be produced in-situ by the well known reaction ofwater, which added to the polyol, with the Isocyanate component of thepolyurethane fomable composition

In yet other embodiments, the invention provides foamable compositionscomprising thermoplastic or polyolefin foams, such as polystyrene (PS),polyethylene (PE), polypropylene (PP) and polyethyleneterphthalate (PET)foams, preferably low density foams. That is, in certain preferredembodiments, the one or more components comprise thermoplasticmaterials, particularly thermoplastic polymers and/or resins. Otherexamples of thermoplastic foam components include.

The present invention also provides go and foams formed there from,preferably low-density foams. In certain embodiments, the thermoplasticfoamable composition is an extrudable composition.

It will be appreciated by those skilled in the art, especially in viewof the disclosure contained herein, that the order and manner in whichthe blowing agent of the present invention is formed and/or added to thefoamable composition does not generally affect the operability of thepresent invention. For example, in the case of extrudable foams, it ispossible that the various components of the blowing agent, and even thecomponents of the present composition, not be mixed in advance ofintroduction to the extrusion equipment, or even that the components arenot added to the same location in the extrusion equipment. Thus, incertain embodiments it may be desired to introduce one or morecomponents of the blowing agent at first location in the extruder, whichis upstream of the place of addition of one or more other components ofthe blowing agent, with the expectation that the components will cometogether in the extruder and/or operate more effectively in this manner.Nevertheless, in certain embodiments, two or more components of theblowing agent are combined in advance and introduced together into thefoamable composition, either directly or as part of premix which is thenfurther added to other parts of the foamable composition.

The invention also relates to foam, and preferably closed cell foam,prepared from a polymer foam formulation containing a composition of theinvention, preferably as part of blowing agent.

Other uses of the present compositions include use as solvents forexample as supercritical or high pressure solvents, deposition agents,as a carrier or part of delivery system for flavor formulations andfragrance formulations extractants of fragrances, including from plantmatter, cleaning agents, and the like. Those of skill in the art will bereadily able to adapt the present compositions for use in suchapplications without undue experimentation.

EXAMPLES

The invention is further illustrated in the following examples, whichare intended to be illustrative, but not limiting in any manner.

Example 1

The bubble (Px) and dew (Py) pressures of various mixtures oftrans-HFO-1234ze and CO₂ are given below at 32° F. (FIG. 1) and 100° F.(FIG. 2), as function of CO₂ mole fraction (composition). The fact thatthese pressures for any of the mixture compositions are intermediatebetween that of the pure components and are neither above nor belowthose of the pure components indicates that these compositions arenon-azeotropic.

Comparative Example 1

This example illustrates the performance characteristics of a heattransfer fluid consisting of certain preferred compositions of thepresent invention compared to that of R-507A and R-404A, tworefrigerants commonly used in low temperature and commercialrefrigeration.

The test conditions are as follows: Mean Evaporator temp −30° F. MeanCondenser temp 100° F. Compressor displacement 10 ft3/minThe results are illustrated in FIG. 3. Under the conditions of thepresent test, it is observed that a good capacity match is obtained by apreferred composition of the present invention in comparision to R-404Aand R-507A (also known as AZ-50) at 8 to 14 wt % CO₂ (92 to 86 wt %transHFO-1234ze) composition.

Comparative Example 2

This example illustrates the performance characteristics of a heattransfer fluid consisting of preferred compositions of the presentinvention compared to that of R-410A (also known as AZ-20), R-407C andR-22, three refrigerants commonly used in air conditioning, heat pumpsand chillers. The test conditions are as follows: Mean Evaporator temp35° F. Mean Condenser temp 110° F. Compressor displacement 10 ft3/minThe results are given in FIG. 4. Under the conditions of the presenttest, it is observed that a good capacity match is obtained with R-22and R-407C in comparison to certain preferred compositions of thepresent invention, namely 8 to 16 wt % CO₂ (92 to 84 wt % HFO-1234ze),and that a good capacity match is obtained with R-410A (also known asAZ-20) in comparison to certain preferred compositions of the presentinvention, namely, 20 to 35 wt % CO₂ (80 to 65 wt % transHFO-1234ze).

It is apparent that many modifications and variations of this inventionas hereinabove set forth may be made without departing from the spiritand scope thereof. The specific embodiments are given by way of exampleonly and the invention is limited only by the terms of the appendedclaims.

Example 2

The bubble (Px) and dew (Py) pressures of various mixtures oftrans-HFO-1234yf and CO₂ are given below at 32° F. (FIG. 1) and 100° F.(FIG. 2), as function of CO₂ mole fraction (composition). The fact thatthese pressures for any of the mixture compositions are intermediatebetween that of the pure components and are neither above nor belowthose of the pure components indicates that these compositions arenon-azeotropic.

Comparative Example 1

This example illustrates the performance characteristics of a heattransfer fluid consisting of certain preferred compositions of thepresent invention compared to that of R-507A and R-404A, tworefrigerants commonly used in low temperature and commercialrefrigeration.

The test conditions are as follows: Mean Evaporator temp −30° F. MeanCondenser temp 100° F. Compressor displacement 10 ft3/minThe results are illustrated in FIG. 3. Under the conditions of thepresent test, it is observed that a good capacity match is obtained by apreferred composition of the present invention in comparision to R-404Aand R-507A (also known as AZ-50) at 5 to 12 wt % CO₂ (95 to 88 wt %HFO-1234yf) composition.

Comparative Example 2

This example illustrates the performance characteristics of a heattransfer fluid consisting of preferred compositions of the presentinvention compared to that of R-410A (also known as AZ-20), R-407C andR-22, three refrigerants commonly used in air conditioning, heat pumpsand chillers. The test conditions are as follows: Mean Evaporator temp35° F. Mean Condenser temp 110° F. Compressor displacement 10 ft3/minThe results are given in FIG. 4. Under the conditions of the presenttest, it is observed that a good capacity match is obtained with R-22and R-407C in comparison to certain preferred compositions of thepresent invention, namely 5 to 10 wt % CO₂ (95 to 90 wt % HFO-1234yf),and that a good capacity match is obtained with R-410A (also known asAZ-20) in comparison to certain preferred compositions of the presentinvention, namely, 15 to 25 wt % CO₂ (85 to 75 wt % HFO-1234yf).

It is apparent that many modifications and variations of this inventionas hereinabove set forth may be made without departing from the spiritand scope thereof. The specific embodiments are given by way of exampleonly and the invention is limited only by the terms of the appendedclaims.

1. A composition comprising from about 1 to about 40 percent by weightof carbon dioxide (CO₂) and from about 60 to about 99 percent by weightof one or more compounds of Formula I, XCFzR3-z (I), where X is a C₂ ora C₃ unsaturated, substituted or unsubstituted, alkyl radical, each R isindependently Cl, F, Br, I or H, and z is 1 to
 3. 2. The composition ofclaim 1 wherein said one or more compounds of Formula I comprises1,1,1,3-tetrafluoropropene (HFO-1234) and wherein said composition has avapor pressure of at least about 30 psia at 35° F.
 3. The composition ofclaim 1 wherein said one or more compounds of Formula I comprises1,1,1,3-tetrafluoropropene (HFO-1234ze).
 4. The composition of claim 3wherein said one or more compounds of Formula I comprisestrans-1,1,1,3-tetrafluoropropene (transHFO-1234ze) and wherein saidcomposition has a vapor pressure of at least about 30 psia at 35° F. 5.The composition of claim 2 wherein said CO₂ is present in an amount ofat least about 5 percent by weight and saidtrans-1,1,1,3-tetrafluoropropene is present in an amount not greaterthan about 95 percent by weight.
 6. The composition of claim 1 whereinsaid one or more compounds of Formula I comprises1,1,1,2-tetrafluoropropene (HFO-1234yf) and wherein said composition hasa vapor pressure of at least about 30 psia at 35° F.
 7. The fluid ofclaim 6 wherein said CO₂ is present in an amount of at least about 3percent by weight and said trans-1,1,1,2-tetrafluoropropene is presentin an amount not greater than about 97 percent by weight.
 8. Thecomposition of claim 1 wherein said composition is non-flammable.
 9. Thecomposition of claim 1 and further comprising at least one adjuvantselected from the group consisting of supplemental lubricants,compatibilizers, surfactants, supplemental flame suppressants,solubilizing agents, dispersing agents, cell stabilizers, cosmetics,polishing agents, medicaments, cleaners, fire retarding agents,colorants, chemical sterilants, stabilizers, polyols, polyol premixcomponents and combinations of two or more of these.
 10. A heat transfercomposition comprising the composition of claim 1 and further comprisingat least one lubricant.
 11. The heat transfer composition of claim 10wherein said lubricant is selected from the group consisting of mineraloil, silicone oil, polyalkyl benzenes (PABs), polyol esters (POEs),polyalkylene glycols (PAGs), polyalkylene glycol esters (PAG esters),polyvinyl ethers (PVEs), poly(alpha-olefins) (PAOs), and combinations ofthese.
 12. The heat transfer composition of claim 10 further comprisingat least one compatibilizer.
 13. The heat transfer composition of claim12 comprising from about 0.5 to about 5 percent by weight of said atleast one compatibilizer.
 14. The heat transfer composition of claim 12wherein said lubricant is present in an amount of from about 5 to about50 percent by weight of the heat transfer composition.
 15. The heattransfer composition of claim 10 further comprising one or moresupplemental flame suppressants.
 16. The heat transfer composition ofclaim 15 wherein said one or more flame suppressant(s) together arepresent in an amount of from about 0.5% to about 30% by weight of theheat transfer composition.
 17. A refrigerant comprising the heattransfer composition of claim
 10. 18. A refrigeration system comprisinga heat transfer composition of claim
 17. 19. A refrigeration system ofclaim 18 selected from group consisting of automotive air conditioningsystems, residential air conditioning systems, commercial airconditioning systems, residential refrigerator systems, residentialfreezer systems, commercial refrigerator systems, commercial freezersystems, chiller air conditioning systems, chiller refrigerationsystems, heat pump systems, and combinations of two or more of these.20. A blowing agent comprising a composition of claim
 1. 21. A blowingagent of claim 20 wherein said compound of formula I and said CO₂together comprise at least about 5% by weight of the blowing agent. 22.A blowing agent consisiting essentially of one or more compounds offormula I and CO₂
 23. A foamable composition comprising the blowingagent of claim
 22. 24. The foamable composition of claim 23 wherein saidone or more components capable of forming foam comprise one or morecomponents capable of forming foam are selected from the groupconsisting of thermoplastic foams, polystyrene foams, polyethylenefoams, low density polyethylene foams, extruded thermoplastic foams,polyurethane foams, polyisocyanurate foams and phenolic foams.
 25. Thefoamable composition of claim 23 further comprising at least oneadditive selected from the group consisting of dispersing agents, cellstabilizers, surfactants, flame retardants and combinations of two ormore of these.
 26. A foam formed from the foamable composition of claim25.
 27. A closed cell foam comprising the foam of claim
 26. 28. A methodof replacing an existing refrigerant contained in a refrigerant systemcomprising removing at least a portion of said existing refrigerant fromsaid system and replacing at least a portion of said existingrefrigerant by introducing into said system a refrigerant compositioncomprising a composition of claim
 1. 29. The method of claim 28 whereinsaid existing refrigerant is selected from the group consisting ofHFC-134a, R-12, R-404A, R-500, HFC-152a, HFC-125, HFC-143a, HFC-32,HCFC-22, R-407C and R-410A and combinations of these.
 30. The method ofclaim 30 wherein said existing refrigerant is selected from the groupconsisting of R-407C, R-404A, R-410A, HCFC-22 and combinations of these.31. The method of claim 29 wherein said existing refrigerant is selectedfrom the group consisting of HFC-134a, HFC-143a, HFC-125, HFC-32 andcombinations of these.
 32. The method of claim 28 wherein said existingrefrigerant system comprises at least a first compressor having a firstdisplacement and further comprising the step of removing said firstcompressor from the system and inserting in said system at least asecond compressor having a larger displacement than said firstcompressor.
 33. The method of claim 28 wherein said existing refrigerantsystem is selected from the group consisting of automotive airconditioning systems, residential air conditioning systems, commercialair conditioning systems, residential refrigerator systems, residentialfreezer systems, commercial refrigerator systems, commercial freezersystems, chiller air conditioning systems, chiller refrigerationsystems, heat pump systems, and combinations of two or more of these.34. The method of claim 28 wherein the capacity of the system after saidreplacement step is at least about at least about 90% of the systemcapacity prior to said removal step.
 35. The method of claim 28 whereinthe mass flow of the system after said replacement step is at leastabout at least about 90% of the mass flow of the system prior to saidremoval step.
 36. The method of claim 28 wherein said refrigerant inaccordance with claim 10 has a Global Warming Potential (GWP) of notgreater than about
 1000. 37. A sprayable composition comprising amaterial to be sprayed and a propellant comprising the composition ofclaim
 1. 38. The sprayable composition of claim 37 in the form of anaerosol.
 39. The sprayable composition of claim 38 wherein said materialto be sprayed is selected from the group consisting of cosmetics,cleaning solvent, lubricants and medicinal materials.
 40. The sprayablecomposition of claim 39 comprising a medicinal material and wherein saidmedicinal material is a drug or a biologically active material.
 41. Amethod of sterilizing an article comprising contacting said article witha composition comprising the composition of claim
 1. 42. A method forcooling an article which comprises condensing a composition of claim 1and thereafter evaporating said composition in the vicinity of thearticle to be cooled.
 43. A method for heating an article whichcomprises condensing a composition of claim 1 in the vicinity of thearticle to be heated and thereafter evaporating said refrigerantcomposition.
 44. The composition of claim 1 in the form of a heattransfer fluid having a refrigeration capacity substantially matchingthat of R-22.
 45. The composition of claim 1 in the form of a heattransfer fluid having a refrigeration capacity substantially matchingthat of R-407C.
 46. The composition of claim 1 in the form of a heattransfer fluid having a refrigeration capacity substantially matchingthat of R-410A.
 47. The composition of claim 1 in the form of a heattransfer fluid having a refrigeration capacity substantially matchingthat of R-404A.
 48. The composition of claim 1 in the form of a heattransfer fluid having a refrigeration capacity substantially natchingthat of R-507A.
 49. A process for changing the heat content of a bodycomprising providing the composition of claim 1 and transferring heatbetween said composition and said body.
 50. An improved heat transfersystem comprising at least one heat transfer fluid and one or morevessels for evaporating and condensing the heat transfer fluid, theimprovement characterized by said at least one heat transfer fluid beinga non-flammable fluid consisting essentially of one or more compounds ofFormula I XCFzR3-z (I), where X is a C₂ or a C₃ unsaturated, substitutedor unsubstituted, alkyl radical, each R is independently Cl, F, Br, I orH, and z is 1 to 3 and carbon dioxide (CO₂).
 51. A sprayable compositioncomprising a material to be sprayed and a propellant comprising anazeotrope-like composition of claim
 1. 52. A sprayable compositionaccording to claim 51 wherein the sprayable composition is an aerosol.53. A sprayable composition according to claim 51 wherein the sprayablematerial is a drug or a biologically active material.
 54. A sprayablecomposition according to claim 51 wherein the sprayable material is amedicinal material such as anti-asthma and anti-halitosis medications.